Basic anthraquinone dyes, with pyridinium 2- or 4-dimethylene group

ABSTRACT

Basic anthraquinone dyes free from sulphonic acid groups produced with a vinylpyridine group which are highly suitable for dyeing and printing acrylonitrile polymers or copolymers.

United States Patent 'Altermatt et 2].

BASIC ANTHRAQUINONE DYES, WITH PYRIDINIUM 2- OR 4-DIMETHYLENE GROUP Inventors:

Roland Entschel, Basel; Curt Mueller, Binningen, Basel-land; all of Switzerland Assignee: Sandoz Ltd., Basel, Switzerland Filed: Aug. 20, 1969 AppL No.: 851,743

Related US. Application Data Continuation-in-pa 't of Ser. No. 481,404, Aug. 20, 1965, Pat. No. 3,518,247.

U.S. Cl. .1...260/294.8 B, 260/250, 260/256.4 B, 260/283 S, 260/286 Q, 260/295 T, 260/296 T, 260/303, 260/307.5, 260/309, 260/309.2, 260/371,

Rudolf Altermatt, Tecknau, Basel-land;

[ 51 June 20,1972

Primary E.\'aminerAlan L. Rotman Attorney-Littlepage, Quaintance, Wray & Aisenberg [57] ABSTRACT Basic anthraquinone dyes free from sulphonic acid groups produced with a vinylpyridine group which are highly suitable for dyeing and printing acrylonitrile polymers or copolymers.

13 Claims, No Drawings ylquinoline,

BASIC ANTHRAQUINONE DYES, WITH PYRIDINIUM 2- R 4-D1METHYLENE GROUP The present application is a continuation-in-part of our copending application Ser. No. 481,404, filed on Aug. 20, 1965, now US. Pat. No. 3,518,247 and relates to basic anthraquinone dyes, their production and use.

These basic anthraquinone dyes are free from sulphonic acid groups and are of the formula R2 th Main-(Q) A where A represents the residue of an anthraquinone dye that is free from sulphonic acid groups,

R represents a hydrogen atom or an alkyl radical which preferably contains one to four carbon atoms,

R represents a hydrogen atom or an alkyl radical which preferably contains one to four carbon atoms,

y represents the direct-bond or a bivalent radical,

Z represents a member of a cyclic system of aromatic character consisting of several, preferably or 6 members, which contains at least one quaternary nitrogen atom and may contain further hetero atoms and further substituents and which may be condensed with further cycloaliphatic, heterocyclic or aromatic rings,

n l or 2 and A e is n nes,

According to the present process n mol (5) of a compound of the formula is/are added on to one mol of a compound of the formula where B has the meaning given above for A or represents the residue of a compound capable of forming an anthraquinone dye residue A. in the above formula (1H) Z has the meaning given above for Z or it represents a member of a cyclic system of aromatic character consisting of several members, which contains at least one quatemizable nitrogen atom and may contain further hetero atoms and further substituents and which may be condensed with further cycloaliphatic, heterocyclic or aromatic rings, and when B in the reaction product represents the residue of a compound capable of forming an anthraquinone dye B is so converted and, if desired or required, the reaction product is quatemated. The quatemation and the conversion into a dye may be performed in either order of succession.

Compounds of the formula (IH) are, for example: 2-vinylpyridines or 4-vinylpyridines; 4-vinylpyrimidine, 2-vinylquinoline, l-vinylisoquinoline, 4-vinylquinoline, 3-vinylquinaldine, 2-vinylthiazole, 2-vinylbenzthiazole, 4-methyl-2-vinylthiazole; 4,5-dimethyl-2vinylthiazole, 4-phenyl-2-vinyltl'1iazole, 4- methyl-2-(a-methylvinyl)-thiazole, Z-vinylbenzimidazole, 2- vinylbenzoxazole, 2-vinylimidazole, l methyl-Z- vinylimidazole, 5-ethyl-2-vinylpyridine, 2-methyl-4-vinylthiazole, 2-propenylpyridine; 4-propenylpyridine, 2-propenylquinoline, 2-propenylpyrimidine, 4-propenyl-2-phen- 2-methyl-5-vinylpyridine, 2-methyl-6-vinylpyridine and 2-vinylpyrazine.

The dye residue A of the aforementioned dyestuffs may contain additionally a cycloimmonium group or an external ammonium, isothiouronium or hydrazinium group.

Dyes that contain at least one of the aforementioned groups have been described, for example, in German specifications v No. 1,011,396 and No. 1,044,023, in German Auslegeschrift No. 1,045,969, in Belgian specifications No. 630,895, No. 633,477, No. 638,438, No. 639,981 and No. 645,280, in French specification No. 1,325,176 and in French Patent of Addition No. 81,967 to French specification No. 1,325,176.

Compounds B may be those which contain a functional group or a group convertible thereinto or a reactive hydrogen atom, the said compound being reacted with a component used for synthesizing the anthraquinone dye residue A, for example by way of a condensation reaction.

Some of the new dyes or some intermediates suitable for forming these dyes can be obtained, for example, by first adding a compound of the formula (111) on to ammonia or a primary amine to form a compound of the formula where R represents a hydrogen atom or a possibly substituted hydrocarbon residue, for example a possibly substituted alkyl, aryl (such as phenyl or naphthyl), aralkyl or cyclohexyl radical. whereupon the resulting compound of the formula (IV) is reacted with a dye or dye intermediate containing reactive group, for example a group capable of condensation such, for example, as an --SO Cl, SO Br, COCl or COBr group.

The aforementioned additive reaction may also be performed with salts of ammonia or of primary amines.

The symbol A may represent an organic or inorganic ion, for example methylsulphate, sulphate, disulphate, perchlorate, phosphotungstic molybdate, benzenesulphonate, 4-chlorobenzenesulphonate, oxalate, maleinate, acetate, propionate, methanesulphonate, chloroacetate, benzoate or complex anions, for example the anion of zinc chloride double salts.

Particularly suitable bridge members y are the atomic groupings:

hydrocarbon residue N-, NH-, o, spossible linked through alkylene, alkenylene, aralkylene, arylene such, for example as (0H),,0-, -(OH2),,s-, (CHzh-JIT- -(CH2)p-OOI| I- where p is a number from 0 to 3 and R represents a hydrogen atom or a lower unsubstituted or substituted alkyl radical or an unsubstituted or substituted aryl or acyl radical.

Possibly substituted hydrocarbon residues are possibly substituted alkyl, phenyl, naphthyl or cycloalkyl radicals such, for example, as methyl, ethyl, propyl, butyl, hydroxyethyl, chloroethyl, cyanethyl, cyclohexyl and the like.

Preferred acyl radicals correspond to the formula where R represents hydrogen or an aromatic or a saturated or unsaturated aliphatic or cycloaliphatic residue. Suitable acyl radicals are, for example, formyl, acetyl, propionyl, butyryl, acryloyl, cyanoacetyl, dimethylaminoacetyl, methylsulphonyl or a possibly substituted phenylsulphonyl ou AllZylating agents suitable for the quaternation of the hetero ring are, for example, esters of strong mineral acidsand of organic sulphonic acids, such as alkylchlorides, alkylbromides and alkyliodides or alkylsulphates, such, for example, as methyl iodide, methyl bromide, methyl chloride, dimethyl sulphate, aralkyl halides; a-halogenated esters of lower alkanesulphonic acids, such, for example, as methanesulphonic, ethanesulphonic or butanesulphonic acid; and esters of benzenesulphonic acids which may be further substituted, such as methyl, ethyl, propyl and n-butyl esters of benzenesulphonic acid, of 2- or 4-methylbenzenesulphonic acid, 4-chlorobenzenesulphonic acid or 3- or 4- nitrobenzenesulphonic acids. Alkylation is preferably performed in an inert solvent or alternatively in an aqueous suspension, or in the absence of a solvent in an excess of the alkylating agent at a temperature above -l C, and, if desired, in a buffered medium. The reaction of a compound of the formula (II) with a compound of the formula (III) is advantageously performed, if desired or required, in the heterogeneous liquid phase in the presence of a. catalyst, for

example of a saturated fatty acid containing one to about five carbon atoms, such as formic, acetic, propionic, butyric or isobutyric acid; their alkyl esters such as ethyl acetate or ethyl propionate; their anhydrides such as acetic or propionic anhydride, or their heavy -metal salts, such as copper, zinc, cobalt or nickel forrnate or acetate; of a polyol such as glycerol; a glycol such as ethyleneglycol; a phenol itself, metacresol or para-cresol or a cresol mixture; of an alcohol; or of a salt of a strong acid with an amine or ammonia, for example ammonium chloride, or aniline hydrochloride; in certain cases even water may act as a catalyst. When both compounds (II) and (III) are, at the reaction temperature, liquid or capable of dissolving or liquefying each other, the process may be performed without a solvent in the presence of 0.1 percent of catalyst, or a solvent may be used additionally. Suitable solvents are the aforementioned catalysts, provided they are liquid and do not cause any side reaction, for example an acylation of an amino group, as well as inert solvents, such as aromatic hydrocarbons which may contain halogen atoms or nitro or alkoxy groups. When solid starting materials are used, a solvent is, in most cases, absolutely necessary to ensure smooth progress of the reaction. Suitable temperatures are within the range from about 50 to 150 C, preferably from about 80 to 130 C; they depend on the reactivity of the reac tants and on the catalyst used When acetic acid of 100 percent strength is used, the most favorable temperature range is from 100 to 120 C, the reaction taking a few hours under these conditions.

The resulting dyes or intermediates can be isolated and, if necessary purified, by conventional basic operations, such as evaporation, precipitation, distillation, filtration, decantation or the like; if they are obtained in a sufficiently pure form, they can be used as they are.

The group of, formula arylor -4-alkyla.minoanthraquinones, in which the anthraquinone and/or the alkylarnino or arylamino residue,

e.g., the phenylamino or naphthylamino residue, may carry further substituents, e.g. possibly substituted alkyl; alkoxy; hydroxyl; halogen, such as chlorine, bromine or fluorine; nitro sulphonamine; sulphone; alkylsulphonyl; azoamino or acylamino; cyclohexyl or cyclohexylamino or similar groupings.

In the anthraquinone compounds the grouping of formula (V) may be attached to the anthraquinone molecule, for example, through a nuclear-bound amino group, for example Alternatively, the grouping of formula (V) may be bound to the anthraquinone molecule, for example, as follows:

where W stands for O or -S-. Good dyes are of the formula in which R stands for N Harylene- 0 H NHarylene- C1, N H-arylene CHz-NH-T Gil R stands for a low molecular alkyl radical, which may be substituted, and contains one to six or, preferably one to four carbon atoms, e.g. CH -C H -C,H,-OH, 30

A ffissnion: and where the dye of formula (X) contains one group of formula (X1) or (Xll).

Equally good dyes are of formula (X) or formula (Xlll), respectively, where the aryl or arylene in formula (X) stands for a phenyl or a phenylene radical.

Especially good dyes are of the formula CH3 C? Y O NH or NHT1 R stands for OE, NH-OH -NHO or NHT1 R stands for R stands for where T p ent swap 9 emale. 4

where T,, stands for -CH3 or CQHB;

l0 and where the dye of Formula (XIV) contains one group of Formula (XV) or (XVI).

(XVl) Equally good dyes are of the formula R73 0 NH2 Rro l l 20 RM l) Rn xvn Where R stands for OCH CHrNHT 0-CHz-CHz-NH-T R stands for S 02NHT1 0H, -NHI1 or NH( g g R stands for H, NH or NHT R stands for l[ or OI'I, whereT stands for a group of Formula (XV) o1 (XVI) and whore tho dye of Formula. (XVII) contains one group of Formula (XV) or (XVI).

The new anthraquinone dyes are used primarily for dyeing, padding or printing fibers, filaments or textile materials made therefrom, which consist of or contain acrylonitrile polymers or copolymers. The dyeings obtained are deep, have good fastness to light and wet treatments with especially good fastness to washing, perspiration, sublimation, pleating, decatising, ironing, water, sea water, dry cleaning, cross-dyeing and solvents. In addition, they display good stability in the presence of salt and are readily soluble, especially in water.

The term acrylonitrile polymers denotes all such polymers which contain more than 80 percent of acrylonitrile. Acrylonitrile copolymers normally consist of 80 to 95 percent of acrylonitrile and 20 to 5 percent of vinyl acetate, vinyl pyridine, vinyl chloride, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters or the like.

The aforementioned fibers can be dyed in mixture with others. In general, dyeing is carried out in an aqueous alkaline, neutral or acidic medium at temperatures of 80 to 100 C, advantageously at the boil, or at temperatures above 100 C under superatmospheric pressure.

The dyeings obtained by the present process are very level, even when no retarder is used. Blend fabrics containing a component of polyacrylonitrile fiber are also well suited to dyeing by the present process. The dyes of the above definitions are also suitable for the mass dyeing of polyacrylonitrile in shades fast to light and wet treatments, and for the coloration of oils, paints, plastics and spun dyed filaments, as well as polyesters or polyolefines modified by acid groups. The new dyes may further be used for dyeing cotton, wool, silk, cellulosic fibers, polyamide fibers and paper at any stage of manufacture, as well as leather. It has been found advantageous to use mixtures of two or more dyestuffs of formula (I).

In the following Examples the parts and percentages are by weight.

EXAMPLE 1 Three hundred and ten Parts of l-amino-4- methylaminoanthraquinone are added to a solution of 150 parts of 2-vinylpyridine in 500 parts of glacial acetic acid, and the resulting suspension is heated to 120 C and stirred for 6 hours at 120 C.

When the reaction is complete, the batch is allowed to cool to 30 C and diluted with 1,000 parts of water. The precipitated dye is filtered off, washed with cold water and dried. For quatemation 10 parts of the dry dye are pasted in 40 parts of dimethylfonnamide, 3.7 parts of dimethylsulphate aminoanthraquinone are entered, followed by 18 parts of 2- .vinylpyridine. The reaction is conducted for 12 hours at 110 cabinet.

On fabrics of polyacrylonitrile fiber this dye produces greenish blue dyeings which show outstandingly good allare added, and the mixture is stirred for 20 hours at 40 c and 15 round fasmm then poured into 500 parts of water. The resulting solution is MPLE 4 are this?"eastwards: w re parts 0 -viny pyn me are reacte in p o ace ic polyacrylonitrile fibers in level blue shades with good fastness acid for 12 hours at C with stirring By f l dropwise properties EXAMPLE 2 addition of water the product is precipitated in a well filterable A Suspension of 86 parts of Lmeth lamine 4 (4, form. After washing for neutralization and drying, 15 parts of aminophenylamino)-anthraquinone in 200 pti rts of glacial gg guattimated ggo c of dlmethyl Sulphate o in parts 0 nitro nzene at fg g jgfi figsgwz On polyacrylonitrile fibers this dye gives dyeingsfof brilliant ditive reaction is complete which can be verified by chroviolet Shade whlch have ggzfggfg and wet asmess' matography the reaction mixture is diluted with a solution of 200 parts of glacial acetic acid in 400 parts of water, and at A suspfmslon of pal-ts of l ammo i C the precipitated dye of the formula phenylammoamhmqimon? m 180 parts acetlc. i 30 prepared at 110 C, in which 25 parts of 2-vinylpyridine are entered. The reaction mixture is maintained for 20 hours at 110 C with stirring, until a chromatogram indicates the end- NIH-OH point of the reaction. The product is precipitated by slow A dropwise addition of 250 parts of 30 percent acetic acid and is then filtered off, washed until of neutral reaction and dried.

Subsequently it is reacted with dimethyl sulphate to the Y quatemated dye, which dyes polyacrylonitrile fabrics in blue I shades of very good all round fastness. NH NH CHZ OH V The following table lists further dyes of this invention which W 40 are produced in accordance with Examples 1 to 5; they correspond to the general formula is suctioned off washed with cold water and dried. The dye is Bar 0 R30 quaternated as described in Example 1; on polyacrylonitrile I H fibers it gives fast dyeings of greenish blue shade.

DYEING EXAMPLE 20 parts of the dye obtained as described in Example 1 are R R Anion 9 intimately mixed with 80 parts of dextrin for 48 hours in a ball 8a mill. One part of the resulting preparation is pasted with 1 part 50 where the symbols R to R have the meanings shown in the of a 40 percent acetic acid solution, the magma is covered table The anion A may be anyone of those mentioned in the with 400 parts of distilled water heated at 60 C while being specification. The symbols T and T appearing in the followcontinuously agitated, and the whole is boiled for a short time. ing table signify: It is diluted with 7,600 parts of distilled water, 2 parts of glacial acetic acid are added, 100 parts of polyacrylonitrile fabric q; 9 then are entered into this dyebath at C. (The Tm the grouping ABET-CH- A polyacrylonitrile fabric had been pretreated for 10 to 15 (1: minutes at 60 C in a bath of 8,000 parts of water and 2 parts v H! of glacial acetic acid). The bath is raised over 30 minutes to 1 100 C and held at the boil for 1 hour. The fabric is then 60 Tn-ths grouping -CH2CH2 BN OH 9 rinsed. The resulting level blue dyeing has good fastness prop ti s "5 EXAMPLE 3 In each example shown in the table the residue T may be In 50 parts of acetic acid 31.4 parts of l-amino-fl henyl replaced by T and vice versa.

TABLE Shade obtained on poly- EX iiiii' N0. R30 R31 R32 R33 R34 fibl'BS 6 H HNT10 H H Greenish HN-CH3 blue.

7 NH O (I II HNTii H H D0.

EXAlVlPE 1;

N-(lower)alkylpyridinium, the dimethylene of which is bound to the anthraquinone nucleus through an amino nitrogen and the lower alkyl of which is substituted or unsubstituted, any substituent of substituted lower alkyl being a member selected from the group consisting of -OH and CO-NH 2. Basic anthraquinone dye according to claim 1 wherein the pyridinium.

3. Basic anthraquinone dye according to claim 1 wherein the pyridinium.

4. Basic a-aminoanthraquinone dye according to claim 1 wherein the a-amino nitrogen is bound directly to the dimethylene of the dimethylenepyridinium.

5. Basic dye according to claim 4 substituted in the l-position by a member selected from the group consisting of methylamino, anilino, chloroanilino, cyclohexylamino and hydroxy and in the 4-position by said a-amino nitrogen.

6. Basic anthraquinone dye of claim 1 free from sulphonic acid groups and of the formula in which R is a member selected from the group consisting of NH OH, Nl-l-CH -NHC H cyclohexylamino, toluidino, xylidino and chloroanilino;

R is a member selected from the group consisting of I-l,

bromo, methyl, ethoxy and methoxyphenyl;

R, is v R, is a member selected from the group consisting of H,

NH OH and anilino;

R is a member selected from the group consisting of H,

OH and anilino;

T is a member selected from the group consisting of 2- dirnethylene-N-(lower)alkylpyridiniurn and 4- dimethyleneN-(lower)alkylpyridinium and A is an acid anion 7. Basic anthraquinone dye of claim 6 wherein R is I-l.

8. Basic anthraquinone dye of claim 7 wherein each of R and R is H.

9. The basic anthraquinone dye according to claim 5 and of LhEIQEEE EM dimethylenepyridinium is 2-dimethylene-N-methyldimethylenepyridinium is 4-dimethylene-N-methyl- Nit-0H;

10. The basic anthraquinone dye according to claim 5 and sft qmul 11. The basic anthraquinone dye according to claim 5 and PFIEEFEE W w O OH 12. The basic anthraquinone dye according to claim 5 and of the formula 

2. Basic anthraquinone dye according to claim 1 wherein the dimethylenepyridinium is 2-dimethylene-N-methylpyridinium.
 3. Basic anthraquinone dye according to claim 1 wherein the dimethylenepyridinium is 4-dimethylene-N-methylpyridinium.
 4. Basic Alpha -aminoanthraquinone dye according to claim 1 wherein the Alpha -amino nitrogen is bound directly to the dimethylene of the dimethylenepyridinium.
 5. Basic dye according to claim 4 substituted in the 1-position by a member selected from the group consisting of methylamino, anilino, chloroanilino, cyclohexylamino and hydroxy and in the 4-position by said Alpha -amino nitrogen.
 6. Basic anthraquinone dye of claim 1 free from sulphonic acid groups and of the formula
 7. Basic anthraquinone dye of claim 6 wherein R11 is -H.
 8. Basic anthraquinone dye of claim 7 wherein each of R13 and R14 is -H.
 9. The basic anthraquinone dye according to claim 5 and of the formula
 10. The basic anthraquinone dye according to claim 5 and of the formula
 11. The basic anthraquinone dye according to claim 5 and of the formula
 12. The basic anthraquinone dye according to claim 5 and of the formula
 13. The basic anthraquinone dye according to claim 5 and of the formula 